Treatment of hydrocarbon oils



June 25, 1940.

E. D. PHINNEY TREATMENT 0F HYDRCARBON OILS Filed Nov. 30. 1937 Patented June 25, 1940 y e 1 PATENTV ors TREATMENT HYDROCARBON OILS I n A e r Edward `D. Phinney, Mount Vernon, N. Y., as-

v e i signor to Process ManagementCompanyInc., a corporationofDelaware Application November 30,1937, Serial No. 177,197

solaims.` (elliot-49).

oil such as crude petroleum oi1,'reduced lcrude oil or the like is stripped by intimate and direct contact with hot pyrolyzed gases from a" ga'srpyrolysis zone so that substantially all lthe Vaporizable constituents are removed and only avery heavy asphaltic tar is leitv in liqueed form. Ihe vapors are separated into a very heavygasfoil fraction, a lighter gas oil fraction, a heavyn'aphtha fraction, land a distillate containing gasoline constituents.

The very heavy gas oil is passed through a' viscosity breaking Zone wherein the oil is maintained under superatmospheric pressure and relatively high temperature conditions in order to obtain a relatively large yield of gas oil constituents suitable for further cracking to produce gasoline, and a relativelysmall yield of gasoline constituents. The products leaving the viscosity breaking zone are introduced into an evaporator or separating zone where a separation into vapors and liquid residue takes place, the vapors Abeing fractionated to separate a gas oil fraction and a heavy naphtha fraction from a distillate containing gasoline constituents.' The liquid residue or a portion "thereof may be passed to a 4tar flash zone to further separate vapors from a liquid residue, the vapors being condensed and a part used as reflux for the vapors from the viscosity 'breaking zone undergoing fractionation and the rest passed to the evaporator. r'

The gas oil fraction lderived from the heavy charging oil and the gas oil fraction separated from the vapors derived from the viscosity breaking zone are passed through a crackingzone maintained under superatmospheric pressure and 40 high temperature conditions to effect the desired extent of cracking. The products from the cracking zone are passed to a second evaporator or separating Zone for separation -into vapors and a liquid residue.V

The heavy naphtha fraction separated from vapors derived'from the heavy charging'oil and the heavy naphtha separated from vapors derived from the viscosity breaking Zone are passed through a reforming and cracking zonev maintained under superatmospheric pressureiand high temperature conditions to effect the desired extent of cracking and reforming of the ,heavyv naphtha. The products leaving the reforming and cracking Zone are passed `intothe second propane, butane, etc.

lfess toI produce lubricating oil, gasoline,` or gas oil tar residue from the tar flash Zone.

vapors and liquid residue. If'desired, the products from the cracking zone and the products fromy the cracking and reforming Zone may be passed'into separate evaporator or separating zones.

vThe vapors from the second evaporator or sep- "5 e aratingzone are fractionated to's'eparate a dis-Y tillate having the desired boilingrange from condensateoil, thecondensate oil being recycled 1 through the cracking zone `for further cracking -orf the constituents thereof.` The overhead -va- To pors which are condensed to form the desired distillate also contain lighter constituents which are not condensed and which pass oif as gases.

These gases are treated to separate lighter constituents such .as hydrogen and methane from "I5 heavier `hydrocarbon constituents such `as ethane, The heavier hydrocarbon constituents are passed through the gas pyroly'sis zone wherein they are maintained under high 'ing the straight run gasoline with anti-knock "25 compounds.

The lighter gases containing hydrogen and methane are utilized to hydrogenate the tar 'residues collected during the operation of the proclconstituents suitable for further cracking.I The tar residues which may be hydrogenated include the veryl heavy asphaltic tar resulting from the stripping of heavy charging oil,-the tar residues n from the evaporator or separating zones and the 35 These tars may be admixed and passed through a hydrogenation zone where they react with the hydrogen and methane separated as above described to pror duce suitable products, or they may be separately 40 passed through hydrogenation Zones. Instead ofV pyrolyzing the hydrocarbon gases which are collected during theoperation vof the process or which may be supplied from an exterfthe resulting products to strip the heavy charging oil of its lighter constituents leaving a residual oil. In this event, however, the products willbe at a lower temperature than products from a pyrolyzing operation and it maybe necessary to -preheat the heavy charging oil in any suitable manner before it is contacted with the products from the polymerization operation. VThe residual oil may be passed throughthe vviscosity breaking r character ID designates -a crude stripping tower into which a heavy charging oil such as crude petroleum oil, reduced crude oil or the like is introduced by being passed through line l2 by pump I4. yThe heavy charging oil directly and intimately contacts products coming from a gas' pyrolysis zone or coil I6 and in this way the heavy charging oil is stripped so that substantially all `the vaporizable constituents of the charging oil are removed and only a very heavy asphaltic tar is left which is collected in liquefied form at the bottom of crude stripping tower I0. The charging oil and pyrolyzed gases are introduced into the bottom portion of the stripping tower IU. The gas pyrolysis operation wil'libe later described in l more detail.

The vapors resulting from the stripping action are separated into a plurality of fractions includ- `ing a very heavy gas oil, a lighter gas oil fraction,

a heavy naphtha fraction and light overhead vapors which contain gasoline constituents and anti-knock compounds and which pass through The combined evaporator duce gasoline.

line I 8 and then through condenser 29, the distillate being passed to the receiver 22 by pump 24.

The receiver 22 is provided with avaived liquid v outlet 26 and a valved gas outlet 28.

The crude stripping tower I9 is provided with a trapout tray 30 having a hood 32 for collecting the very heavy gas oil, a trapout tray 34 having a hood 36 for collecting the lighter gas oil fraction and trapout tray 38 havingva hood 40 for collecting the heavy naphtha fraction.

The very heavy gas oil collecting on trapout tray 3Bis withdrawn through line '32 and passed through a viscosity breaking zone or coil 44 by pump 46. In this viscosity breaking Zone or coil the heavy oil is subjected to superatmospheric pressure and a relatively. high temperature for a time limited to produce a relatively large amount of intermediate constituents suitable for further cracking under more drastic conditions to pro- During the treatment of the heavy oil in the viscosity breaking zone or coil 44 gasoline constituents are also obtained. The products resulting from the viscosity breaking treatment are passed through line 48 preferably having aA pressure reducing valve 58 kinto the evaporator or separating zone 52 of the combined evaporator and fractionating tower 54 wherein a separation into vapors and liquid residue occurs.

The vapors are fractionated in; the fractionating sections 56 and 58 of the combined evaporator and fractionatingtower 5d lto separate a gas oil fraction suitable for further cracking to produce gasoline constituents and a heavy naphtha fraction from light overhead vapors which are passed through line 69 and then through condenser 52,l

the distillate being passed to the receiver 64 vby pump 66. The receiver 64 `is provided with a valved gas outlet 58 and a valved liquid outlet 70. and fractionating tower 54 is provided with a trapout tray 'I2 having a hood 'I4 for collecting the gas oil fraction and collecting to make high anti-knock gasoline.

8| to further separate vapors from a liquid residue. Some of the pyrolyzed gases from the pyrolysis zone or coil I6 may be diverted through line 82 and introduced into the tar flash tower to further strip the `liquid residue therein. The vapors leave the top of the flash tower 8| through line 83 and are passed through condenser 84,.the distillate being passed through line by pump 8E into the evaporator andv separating zone'52 andthrough line 81 into the fractionating scction 56 as reflux or all the distillate may be passed through one of the lines to the exclusion of the other. l l

lThe gasl oil fraction separated from vapors derived from the heavy charging oil and collecting on trapout tray 34fis withdrawn therefrom through line 88 and the gas oil fraction separated from vapors derived from the viscosity broken vproducts and collecting on trapout tray 'i2 is withdrawn through line 89. These gas oil fractions are preferably admixed and passed through line 901by pump 9| and then through a cracking j Zone or coil 92 in furnace v93 wherein the oil is subjected to high cracking per pass conditions The products from the. cracking Zone or coil 92 are passed through line 94 having a pressure reducing valve 95 intol the second evaporator or separating zone 96 of the combined evaporator and fractionating tower 98wherein a separation into vapors and liquid residue occurs. K

The heavy naphtha fraction separated from vapors derived from the heavy charging oil and collecting on trapout tray 38 in the crude strip ping tower I0 is Withdrawn therefrom and passed i? through line |00 by pump |02 and is admixed with the heavy naphtha fraction separated from vapors derived from the viscosity broken prod` ucts, the latter heavy `naphtha fraction being withdrawn from trapout tray I8 in the combined evaporator and fractionating tower 5d and passed through line |84.by pump |06. The combined stream is `passed through a cracking and reforming Zone or coil |08 wherein it is subjected to superatmospheric pressure and high temperature conditions to effect the desired extent of cracking and reforming of the heavy naphtha fractions. The products from the cracking and reforming zone I08-are passed through line I I8 having a pressure reducing'valve 2 into the separating Zone 96- of the combined evaporator and fractionating tower 98 wherein a separation into vapors and liquid residue occurs. Before being introduced into the evaporator or separating zone 95, the products from the cracking Zone 92 and the cracking and reforming Zone |88 may be quenched with an oil passing through. line I i4.

The vapors separated in the second evaporator 96 arevfractionated in fractionating section II'I of the combined evaporator and fractionating tower 98 to separate light vapors from condensate `oil which is collected on trapout tray I|8 having a hood |20. The condensate oil is preferably withdrawn from trapout tray ||8 and vpassed through line |22 by pump |24 for recycling through the cracking zone'or coil 92. The vapors passing overhead are conducted through line |26 and condenser |29 and the distillate passed to receiver |29 by pump |38. In the receiver |29 vapors and gases are separated from liquid. The. yliquid which is a light motor fuel such as gasoline is withdrawn through valved line |32.

The gases and vapors separated in the distillate receiver'l29 are further treated to separatehydrogen and methane therefrom by sub- -into tower l0.

`jecting the gases and vapors, forY example, to

low temperature fractionation. Other methods of separating such. gases known in prior practices may be used. The gases and vapors may be passed through line |34 and compressed by compressor |35 to liquefy heavier portions thereof and cooled by condenser |31 and then passed to the low temperature fractionating tower |38 held under pressureto separate light gases containing hydrogen and methane from heavier hydrocarbon gases containing ethane and heavier constituents. The heavier hydrocarbon fraction is withdrawn from fractionator |38 and passed through line |40 by pump |42 and through the gas pyrolysis zone or coil I6 wherein the gases are subjected to high temperature and relatively low superatmospheric pressure conditions to crack them and form gaseous unsaturated compounds and normally liquid aromatic .compounds including benzol which latter compounds are valuable as anti-knock constituents and which pass overhead with gasoline constituents leaving the top of crude stripping tower l0 when the hot pyrolyzed gases are introduced The hot pyrolyzed gases Iare passed into the crude stripping tower 0 for stripping the heavy charging oil as above described. If desired, gas from an external source may be passed through line |43 and added to the gas passing through line |40. e

The light gases separated in the fractionator |38 and which contain hydrogen and methane after having preferably been passed through a scrubbing tower to remove impurities are passed through line |44 and are used'to hydrogenate and react with the tar residues obtained during the operation of the process. The heavy asphaltic residue remaining after stripping the heavy oil in stripping tower I0 is withdrawn from the bottom thereof and Lpassed through line |45 by pump |46 and is mixed with the light gases passed through line |44 by pump |41. This mixture is passed through a heating coil |48 wherein it is maintained under high temperature and high pressure conditions. The mixture is then passed to a hydrogenating zone` |49 where it contacts a suitable catalyst under pressure to hydrogenate the heavy or asphaltic residue. A

on the bottom of the tar flash tower 8| is :withdrawn therefrom through line |54 and may be combined with the other tar residues. A portion of this tar residue may be withdrawn from the system through line |56. The liquid residue from the bottom of the second evaporator or separating zone 96 of the second combined evaporator and fractionating tower 98 is withdrawn through linev |58 and may be combined with the other tar residues for further treatment. A portion of the tar residue may be withdrawn from the system through line |59.

The tar residues are mixed with the light gases passing through line |44 and the mixture is passed through the heated coil |48 to raise the temperature ofthe mixture to a. relatively high der `the system pressure to separate liquid from gases. The liquid is withdrawn through line y|64 having a pressure reducing valve |65 intoV a -tion through line |10 suitable for further cracking `in reforming zone |08. The gases from the 'separator |63 are passed overhead through line |1| and a lportion sent to storage or all the gases may be passed-'through line |12 and combined with the gases from the receiver |29 and the mixture passed to the. fractionatingseparator |38.

The vapors leave the top of the fractionating temperature'and then passed through the hyndrogenation zone |49 where it contacts with a suitable catalyst to hydrogenate the tar residues :a's above described, The reaction products leave :the `hydrogenation 'zone through line |6| and condenser |62 and the cooled and condensed `products'are passed to a separating zone |63 untower |66 through line |14 and are condensed by being passed through condenser |16, the disvtillate being passed through line |11 by pump |18 and into a receiver |80.

The receiver is provided with a valved gas outlet A| 8| and a valved liquid outlet |82 through which a light motor fuel such as a .gasoline may be withdrawn. The various liquid residues may be sepa- 'I in the pyrolysis zone I6, I may polymerize the gas mixture by passing it through a heated coil or zone to form normally liquid hydrocarbons containinggasoline constituents. 'Ihe polymerization takes place at higher pressure and at a lower temperature (at about '150 to 1200 F. and at about 400 to 3000 pounds per square inch) than the pyrolysis and therefore it may be necessary to preheat the heavy charging oil before .it is introduced into the crude stripping tower I0. The reaction products from the polymerization treatment are introduced into theA stripping? tower I0 wherein they contact the introduced heavy charging oil. A portion of.. the heavy charging oil will be vaporized and the residual oil which collects on the bottom of the stripping tower is withdrawn through line |45 and passed through line into viscosity breaking zone 44 wherein it is maintained under superatmospherc pressure and elevated temperature for the desired time to produce a relatively large yield of gasoil constituents suitable for further cracking to produce gasoline; When using residual oil from the bottom of the tower l0 no sidey cut is withdrawn from. trapout tray 30 and this tray may be omitted; and no tar or asphalt residue is obtained from the bottom of stripping 'tower 0 as in the case where hot pyrolyzed gases are used.

A typical operation contemplated by my inven- `tion will now be given but it is to be understood that I am not restricted thereto. The heavier lhydrocarbon 4fraction containing ethane,` propane, butan-e, etc., separated in the low temperature fractionator |38 isfpassed through the pyrolysis Zone or coil|6 wherein it is subjected to -a pressure of" about atmospheric' to' 200pounds per square inch and raised'` to va temperature of about 1200 to `1750 F. to effect the desired 'extent of cracking thereof. In this pyrolysis the hydrocarbon gases arer converted into gaseous ,unsaturated compoundsfand normally liquid aromatic compounds including valuable antiknock constituents. The reaction products leave the pyrolysis zone or vcoil at a high temperature and are passed into the stripping tower |'0 wherein they contact the introduced heavy charging oil which preferably. is crude petroleum oil'. The

Vcrude Stripping tower I0 may be maintained at a pressure of aboutv atmospheric to 200 pounds per square inch. Substantially all of the introducedheavy oil is vaporized so that only a very heavy asphaltic residue is left. When using a Mid' Continent crude oil having an A. P. I. gravity of 35, the asphaltic residue has an A. P. I. gravity of about 10 to 15, for example, 12. The reaction products from the pyrolysis Zone or coil I6Y also have a steam stripping effect on the introduced heavy oil charge.

The vaporized heavy charging oil is separated into liquid fractions and a light distillate in the stripping tower l0, the fractions being collected ontrapout trays 30, 34 and 38 and the light distillate being collected in receiver 22. The light distillate contains light aromatic compounds resulting` from the gaspyrolysis and may be mixed `with the nnal distillate withdrawn from receiver |29, or may be used, for example, as a blending stock with other fuels. The very heavy gas oil which collects on trapout tray 30 consists essentially of constituents boiling above 650 -to '750 F'. and is passed through the viscosity break.- ing zone 44 wherein it is maintained' under a pressure of about'lOO to 500 pounds per square inch and at a temperature of about 850 to 950 F. for a time limited to produce a relatively large yield of lighter gas oil constituents which are suitable for further `cracking to produce gasoline.

The products leave the viscosity breaking zone 44 at a temperature, for example, of about 880 F. and at a pressure of about 200 pounds per square inch and are pass-ed to the evaporator or separating zone 52 which is maintained under a pressure of about 10 to 200 poundsV per square inch and the products are separated into aV liquid residue and vapors. The vapors are further fractionated in the fractionating sections 56. and 58 of the combined evaporator and fractionating tower 54 to separate a gas oil fraction which has an end point of about 650 to 750 F..and a heavy naphtha fraction which has .an initial boiling point of about 200 to 300 F. and an end point of about 400 to 500 F. from light overhead vapors.

The gas oil separated from vapors derived from the viscosity broken products collects on trapout tray l2 and is withdrawn therefrom and is .mixed with the gas oil withdrawn from tray 34 which is separated from the vapors 4derived from the heavy charging oil and which has about the same initial boiling point as the gas oil from tray l2. The mixture of gas oils is passed through 1ine'90 and through the cracking zone or coil 92 wherein it is maintained under a pressure of about 500 to 1000 pounds per square inch and at a temperature of about 850 to 1000 F. to effect the desired extent ofcracking of the gas oil constituents to produce the maximum yield of gasoline constituents. The stream of cracked products from thecracking zone or coil l'92 vis passed-through the secondevaporato'r or lseparating zone 96- Which is maintained under a pressure of about 100 to 200 Ypounds per square inch. In the evaporator or separating zone 96 there is a separation of the cracked products into vapors and liquid residue.

`'I'he heavy naphtha fraction separated from .vaporsuderived from the viscosity broken products and the heavy. naphtha Afraction separated from vapors derived from the heavy charging oil 5 and having about the same boiling rangesare admixed and passed through the reforming zone or coil |08 wherein they are maintained underja pressure of about200 to 1000 poundsper square inch and at a temperature of about 950 to 1150" f F. The stream of Ireformed and cracked products is passed' to the second evaporator or separating zone 96 wherein they are separated into vapors and cracked residue.- The vapors derived from products from the crackingzones. 92 and .|08 are fractionated to separate a light distillate having the desired end point which is collected in receiver |29. Vapors leave the Areceiver |29 through-line |34. These vapors are then compressed and cooled to liquefy some of the gases and vapors, and the liquefied mixture is passed to the low temperaturel fractionating zone |38 to separate light gases suchl as hydrogen and methane fromheavy hydrocarbon gases such as ethane, propane, butane,\etc. The vheavy hydrocarbon gases are passed. through the pyrolysis Zone I6 where they are pyrolyzed as above described.

The light gases which contain hydrogen and methane are mixed with. the heavy asphaltic residue withdrawn from the bottomof the stripping tower I0, and the tarresidues withdrawn from the bottoms of the evaporator or separating zone 52, tar flash tower 8| andthe second evaporator or separating4 zone. 96. `The mixture of hydrogenv and tar and asphaltic residues is heated to a temperature of about 700 to 850 F.

in heating coil |48 and passed through the hydrogenation zone |49i wherein themixture is maintained under a pressureof about`3000 to 3600 pounds per square inch and at a temperature of y about '750 to 1000 F. in the presence of a suitable hydrogenating catalyst such as suldes of molybdenum, chromium or tungsten ormixtures thereof to effect theA desired extent of hydrogenating. The products leaving the hydrogenation Zone |49 are cooled and passed through the separating Zone |63 to separate gases and vapors from liquid. The liquid is fractionated in the fractionating tower lb` under lower pressure which comprises intimately contacting a heavy petroleum charging stockwith hot pyrolyzed gases introduced into the bottom "portion of a stripping zone to separate vaporizable, constituents inthe heavy oil from' a heavy asphaltic residue, fractionating the Vapors'in said' stripping zone" to separate fractions Vcomprising heavy gas oil,light gas oil and heavy naphtha, passing heavy gas oil so obtained through a` viscositybreaking zone wherein it is subjected to viscosity breaking conditions of temperature and pressure to effect conversion into a high yield of lower boiling gas oil constituents'l suitable for further 7 cracking to produce gasoline constituents, separating the products from the viscosity breaking zone into vapors and liquid residue, fractionating the vapors in a separate fractionating zone to separate a light vgas oil from. a heavy naphtha fraction, combining the light gas oils and passing the mixture through a gas oil cracking zone wherein the mixture is maintained at cracking conditions of temperature and pressure to effect conversion into gasoline constituents, passing the resultant cracked products to a separating Zone to separate vapors from liquid residue, combining the heavy naphtha fractions and passing,Y

' a light distillate having the desired boiling range and a higher boiling condensate oil, directing said condensate oil to said gas oil cracking Zone, treating said gaseous fraction to separate light V gases containing hydrogen from heavier hydrocarbons comprising ethane, propane and butane, subjecting said heavier hydrocarbonsV to high temperature and superatmospheric pressure conditions to pyrolyse them and directing the resultant hot pyrolyzed gases into said stripping zone for intimately contacting the heavy petroleum. charging stock therein,

2. A method of` converting higher boiling hydrocarbons into lower boiling hydrocarbons which comprises intimately contacting a heavy petroleum charging stock with hot pyrolyzed gases introduced into a stripping Zone to separate vaporizable constituents in the heavy oil from a heavy residue, fractionating the vapors in said stripping zone to separate fractions comprising heavy gas oil and light gas oil, passing resultant heavy gas oil to a viscosity-breaking Zone wherein it is subjected to viscosity-breaking conditions of temperature and pressure to effect conversion into a high yield of lower boiling gas oil constituents suitable for further cracking to produce gasoline constituents, separating the products from the viscosity-breaking zone into vapors and residue, fractionating the vapors in a separate fractionating zone to separate out a fraction comprising light gas oil, vcombining said light gas oil fractions and passingthe mix- `ture through a gas oilv cracking Zone wherein the' mixture is maintained at cracking conditions of v temperature and pressure to eiTect conversion into gasoline constituents, passing the resultant cracked products to a-separating zone to lseparate vapors from liquid residue, fractionating the' vapors from saidseparating zone to form a gaseous fraction, a light distillate having the desired boil-A ing range and a higher boiling condensate oil, directing said condensate oil to saidv gas oil cracking zone, treating saidgaseous fraction to` separate light gases containing hydrogen from heavier.. hydrocarbons comprising ethane, propane and butane, subjecting said heavier hydrocarbons to high temperature and superatmospheric pressure conditions to pyrolyze them and directing the resultant hot pyrolyzed gases into said` stripping zone for intimately contacting the heavy petroleum charging stock therein.

3. A method ofconverting higher boiling hydrocarbons into lower boiling hydrocarbons which comprises intimately contacting a heavy petroleum charging stock with hot pyrolyzed gases .introduced into a stripping zone to sepal 25 rate vaporizable constituents in the heavy oil from a heavy'residue, fractionating the vapors in said stripping zone to separate fractions comprising heavy gas oil and light gas oil, passing resultant heavy gas oil to a viscosity-breaking zone wherein it is subjected to Viscosity-breaking conditions of temperature and pressure to effect conversion into a high yield of lower boiling gas oil constituents suitable for further cracking to produce gasoline constituents, separating the products from the viscosity-breaking zone into desired boiling range from higher boiling hydrocarbons, treating said gaseous fraction to sepa-v rate light gasesl containing hydrogen from` heavier hydrocarbons comprising 'ethane, propane and butane, subjecting said heavier hydrocarbons to high temperature and superatmospheric pressure conditions to pyrolyze them and directing the resultant hot pyrolyzed gases into said stripping zone for intimately contacting the heavy petroleum charging stock therein.

EDWARD. D. PHINNEY. 

